Chemoselective heterogeneous iridium catalyzed hydrogenation of cinnamalaniline
Savela, R., Shcherban, N. D., Melander, M. M., Bezverkhyy, I., Simakova, I. L., Långvik, O., Kholkina, E., Schindler, T., Krauβ, A., Honkala, K., Murzin, D. Y., & Leino, R. (2021). Chemoselective heterogeneous iridium catalyzed hydrogenation of cinnamalaniline. Catalysis Science and Technology, 11(4), 1481-1496. https://doi.org/10.1039/D0CY01886D
Published inCatalysis Science and Technology
© The Royal Society of Chemistry 2021
Selective hydrogenation of unsaturated imines over heterogeneous catalysts is an ecologically feasible and effective way to produce commercially valuable saturated imines and unsaturated amines under mild conditions, avoiding the utilization of toxic halides. The liquid-phase hydrogenation of a model imine, cinnamalaniline, over Ir, Ru, Pd and Au catalysts was studied in polar protic (methanol, 2-propanol), polar aprotic (methyl tert-butyl ether) and non-polar aprotic (toluene) solvents at 40–80 °C under atmospheric hydrogen pressure. Different metal oxides (Al2O3, ZrO2, SiO2) and carbon composites based on carbon nitrides synthesized by pyrolysis of ethylenediamine or melamine modified by KOH, HNO3, NH4Cl or TEOS (including template KIT-6), porous carbon (samples prepared by pyrolysis of sucrose, including template KIT-6) and mesoporous carbon Sibunit were applied to study the effect of the support. Among the tested metals, iridium exhibited the most promising catalytic performance in terms of hydrogenation activity and chemoselectivity towards unsaturated amine. The use of Ir on carbon nitrides (C3N4–NH4Cl, CxNy-KIT-6) and amphoteric metal oxides (ZrO2, Al2O3) in nonpolar aprotic toluene solvent provided the best selectivity towards unsaturated amine by minimizing oligomerization. Computational studies indicate that the selective hydrogenation of the C=N group on Ir results from a favorable cinnamalaniline adsorption geometry at high surface coverage. Comparable heterogeneously catalyzed highly chemoselective hydrogenation of unsaturated imine into unsaturated amine under atmospheric hydrogen pressure and low temperatures has not been reported previously. ...
PublisherRoyal Society of Chemistry
Publication in research information system
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Related funder(s)Academy of Finland
Funding program(s)Postdoctoral Researcher, AoF; Academy Programme, AoF
Additional information about fundingMMM and KH acknowledge funding by the Academy of Finland through projects 307853 and 307623. The computational studies were made possible by the Finnish Grid and Cloud Infrastructure – FGCI. RS acknowledges funding by the Academy of Finland through project 295364. Synthesis of some catalysts (Ir on alumina, zirconia, silica, Sibunit) was supported by RFBR Grant 18-53-45013 IND_a, characterization (TEM, N2 physisorption, XRF) was supported by Ministry of Science and Higher Education of the Russian Federation. NDS acknowledges the support of the National Academy of Sciences of Ukraine to the project “New effective nanoscale catalysts for the production of valuable organic compounds from bio raw materials and products of its conversion” (no. 19/02-2020). ...
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